Curable resin composition, cured product, prepreg, circuit board, build-up film, semiconductor sealing material, and semiconductor device

Abstract

To provide a cured product which is excellent in heat resistance (high glass transition temperature) and dielectric characteristics (low dielectric characteristics), a prepreg, a circuit board, a build-up film and a semiconductor sealing material, which have the performances, and a semiconductor device.SOLUTION: A curable resin composition contains a vinylbenzyl compound having an indan bisphenol skeleton represented by general formula (1), wherein the curable resin composition further contains a polymerization initiator, a content of the polymerization initiator is 50 to 5,000 ppm with respect to the vinylbenzyl compound, and a total chlorine content with respect to the total amount of the vinylbenzyl compound and the polymerization initiator is 100 to 5,000 ppm. There are provided a cured product of the curable resin composition, and a prepreg, a circuit board, a build-up film and a semiconductor sealing material, which use the curable resin composition, and a semiconductor device.SELECTED DRAWING: None

Description

[Technical field]

[0001] The present invention relates to a curable resin composition containing a vinylbenzyl compound having an indane bisphenol skeleton, and to a cured product, a prepreg, a circuit board, a build-up film, a semiconductor encapsulant, and a semiconductor device obtained from the curable resin composition. [Background technology]

[0002] With the increase in the volume of information and communication in recent years, information and communication in the high frequency band has become more prevalent. This has created a demand for electrical insulating materials with better electrical properties, particularly low dielectric constant and low dielectric tangent, in order to reduce transmission loss in the high frequency band.

[0003] Furthermore, printed circuit boards and electronic components using these electrical insulating materials are exposed to high-temperature solder reflow during mounting, so materials with excellent heat resistance and a high glass transition temperature are required. In particular, lead-free solders with high melting points have recently been used from the perspective of environmental issues, so there has been an increasing demand for electrical insulating materials with higher heat resistance.

[0004] In response to these demands, vinyl group-containing curable resins having various chemical structures have been proposed. Examples of such curable resins include divinylbenzyl ether of bisphenol and polyvinylbenzyl ether of novolac (see, for example, Patent Documents 1 and 2). However, these vinylbenzyl ethers cannot provide a cured product with sufficiently small dielectric properties, and the obtained cured product has problems in being used stably in a high frequency band. Furthermore, divinylbenzyl ether of bisphenol does not have sufficiently high heat resistance. [Prior art documents] [Patent documents]

[0005] [Patent Document 1] Japanese Patent Application Publication No. 63-68537 [Patent Document 2] Japanese Patent Application Publication No. 64-65110 Summary of the Invention [Problem to be solved by the invention]

[0006] Therefore, an object of the present invention is to provide a cured product having excellent heat resistance (high glass transition temperature) and dielectric properties (low dielectric properties), and a prepreg, a circuit board, a build-up film, a semiconductor encapsulant, and a semiconductor device that combine these properties. [Means for solving the problem]

[0007] The present invention relates to a curable resin composition containing a vinylbenzyl compound having an indane bisphenol skeleton represented by the following general formula (1), characterized in that the curable resin composition further contains a polymerization inhibitor, the content of the polymerization inhibitor is 50 to 5,000 ppm relative to the vinylbenzyl compound, and the total chlorine content relative to the total amount of the vinylbenzyl compound and the polymerization inhibitor is 100 to 5,000 ppm.

[0008] [ka] (1)

[0009] [In formula (1), X represents a vinylbenzyloxy group. Each Ra independently represents an alkyl group having 1 to 15 carbon atoms, an alkyloxy group, an alkylthio group, an aralkyl group, an aryl group, an aryloxy group, an arylthio group, a cycloalkyl group, a hydrogen atom, a halogen atom, a nitro group, a hydroxyl group, or a mercapto group, and q represents an integer value of 0 to 4. When q is 2 to 4, Ra may be the same or different within the same ring. Each Rb independently represents an alkyl group having 1 to 15 carbon atoms, an alkyloxy group, an alkylthio group, an aryl group, an aryloxy group, an arylthio group, a cycloalkyl group, a hydrogen atom, a halogen atom, a hydroxyl group, or a mercapto group, and r represents an integer value of 0 to 3. When r is 2 to 3, Rb may be the same or different within the same ring. n is the average number of repeating units and represents a numerical value of 0.2 to 20.]

[0010] Another object of the present invention is to provide a cured product of the curable resin composition, and a prepreg, a circuit board, a build-up film, a semiconductor encapsulant, and a semiconductor device using the curable resin composition. Effect of the Invention

[0011] The cured product obtained from the curable resin composition of the present invention has excellent heat resistance and low dielectric properties. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0012] The present invention will be described in detail below.

[0013] The present invention comprises a vinylbenzyl compound having an indane bisphenol skeleton represented by the following general formula (1), a specific amount of a polymerization inhibitor, and a specific total chlorine content.

[0014] [ka] (1)

[0015] In formula (1), X represents a vinylbenzyloxy group. Each of Ra independently represents an alkyl group having 1 to 15 carbon atoms, an alkyloxy group, an alkylthio group, an aralkyl group, an aryl group, an aryloxy group, an arylthio group, a cycloalkyl group, a hydrogen atom, a halogen atom, a nitro group, a hydroxyl group, or a mercapto group, and q represents an integer value of 0 to 4. When q is 2 to 4, Ra may be the same or different in the same ring. Each of Rb independently represents an alkyl group having 1 to 15 carbon atoms, an alkyloxy group, an alkylthio group, an aryl group, an aryloxy group, an arylthio group, a cycloalkyl group, a hydrogen atom, a halogen atom, a hydroxyl group, or a mercapto group, and r represents an integer value of 0 to 3. When r is 2 to 3, Rb may be the same or different in the same ring. n is the average number of repeating units and represents a value of 0.2 to 20.

[0016] The vinylbenzyl compound has an indane skeleton, and therefore the proportion of polar functional groups in the structure of the vinylbenzyl compound is small, so that the cured product produced using the vinylbenzyl compound has excellent dielectric properties. In addition, the vinylbenzyl compound has an indane skeleton, and therefore has excellent flexibility and softness, and is expected to have improved brittleness resistance.

[0017] Ra in the general formula (1) is preferably any one of an alkyl group having 1 to 4 carbon atoms, a cycloalkyl group having 3 to 6 carbon atoms, and an aryl group having 6 to 10 carbon atoms. By using the alkyl group having 1 to 4 carbon atoms, etc., the planarity and crystallinity in the vicinity of the bisphenol group are reduced, which is a preferred embodiment in which the solvent solubility is improved and a cured product can be obtained without impairing the reactivity of the bisphenol group.

[0018] In the general formula (1), q is preferably 1 to 3, and more preferably 2. When the q is 2, the effect of steric hindrance is small, which is a more preferable embodiment in the production (synthesis) of a vinylbenzyl compound having a polyindane bisphenol skeleton.

[0019] In the general formula (1), it is preferable that r is 0 and Rb is a hydrogen atom, and it is also preferable that r is 1 to 3 and Rb is at least one selected from the group consisting of an alkyl group having 1 to 4 carbon atoms, a cycloalkyl group having 3 to 6 carbon atoms, and an aryl group having 6 to 10 carbon atoms. In particular, when r is 0 and Rb is a hydrogen atom, steric hindrance is reduced during the formation of the indane skeleton of the vinylbenzyl compound having an indane bisphenol skeleton, which is advantageous for the production (synthesis) of the vinylbenzyl compound having a polyindane bisphenol skeleton, and is a preferred embodiment.

[0020] In addition, by having a vinylbenzyl group in the general formula (1), high radical polymerizability is exhibited, and not only is it curable alone, but it also becomes possible to blend it with various curing agents, thereby enabling blending according to various required properties.

[0021] The vinylbenzyl compound having a polyindane bisphenol skeleton preferably has a structure represented by the following general formula (2).

[0022] [ka] ····(2)

[0023] In the formula (2), X represents a vinylbenzyloxy group, R1 and R2 each independently represent a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, an aryl group, an aralkyl group, or a cycloalkyl group, provided that R1 and R2 are not both hydrogen atoms at the same time, and n represents the average number of repeating units and is a value of 0.2 to 20.

[0024] <Method of producing indane bisphenol compound> The method for producing the indane bisphenol compound, which is the raw material for the vinylbenzyl compound, will be described below.

[0025] In the following general formula (3), Rc each independently represents a monovalent functional group selected from the group consisting of the following general formulas (4) and (5), and the ortho position of at least one of the two Rc's is a hydrogen atom, and Rb and r are the same as those defined above.

[0026] [ka] (3)

[0027] [ka] (4)

[0028] [ka] (5)

[0029] In the following general formula (6), x is preferably 1 or 2, and more preferably 1. By having a hydroxyl group (phenolic hydroxyl group), it is possible to introduce a phenolic hydroxyl group to the terminal, which is a preferred embodiment. Note that Ra and q are phenol or a derivative thereof, which are the same as above, and an indane bisphenol compound represented by the following general formula (7) can be obtained by reacting a compound represented by the above general formula (3) with a compound represented by the following general formula (6) in the presence of an acid catalyst. Note that Ra, Rb, q, r, x, and n in the following general formula (7) are the same as above.

[0030] [ka] (6)

[0031] [ka] ····(7)

[0032] [ka] (8)

[0033] In the indane skeleton (see general formula (8)) which is a characteristic of the indane bisphenol compound, the average number of repeating units n is 0.2 to 20, preferably 0.5 to 10, and more preferably 1.0 to 8.0, in order to provide a low melting point (low softening point), low melt viscosity, and excellent handleability. The indane bisphenol compound has an indane skeleton in its structure, which provides excellent solvent solubility. If the n is less than 0.2, the content of high melting point substances in the structure of the indane bisphenol compound is high, resulting in poor solvent solubility and a low proportion of high molecular weight components which contribute to flexibility. This is undesirable, as it reduces the brittleness resistance of the cured product obtained by using the indane bisphenol type epoxy resin made from the indane bisphenol compound as a raw material, and may also reduce flexibility and pliability. Furthermore, if the n exceeds 20, the viscosity will increase when dissolved in a solvent, raising concerns that the heat resistance of the resulting cured product will be poor. Furthermore, the amount of high molecular weight components will be too high, raising concerns that the flowability will decrease when the cured product is molded, making the handleability poor, which is undesirable.

[0034] The compound represented by the general formula (3) used in the present invention (hereinafter referred to as "compound (a)") is not particularly limited, but typically, p- and m-diisopropenylbenzene, p- and m-bis(α-hydroxyisopropyl)benzene, p- and m-bis(α-chloroisopropyl)benzene, 1-(α-hydroxyisopropyl)-2-isopropenylbenzene, 1-(α-hydroxyisopropyl)-3-isopropenylbenzene, 1-(α-hydroxyisopropyl)-4-isopropenylbenzene, or a mixture thereof is used. In addition, the nuclear alkyl group-substituted products of these compounds, such as diisopropenyltoluene and bis(α-hydroxyisopropyl)toluene, can also be used, and further, the nuclear halogen-substituted products, such as chlorodiisopropenylbenzene and chlorobis(α-hydroxyisopropyl)benzene, can also be used.

[0035] Other examples of the compound (a) include 2-chloro-1,4-diisopropenylbenzene, 2-chloro-1,4-bis(α-hydroxyisopropyl)benzene, 2-bromo-1,4-diisopropenylbenzene, 2-bromo-1,4-bis(α-hydroxyisopropyl)benzene, 2-bromo-1,3-diisopropenylbenzene, 2-bromo-1,3-bis(α-hydroxyisopropyl)benzene, 4-bromo-1,3-diisopropylbenzene, 4-bromo-1,3-bis(α-hydroxyisopropyl)benzene, 5-bromo-1 ,3-diisopropenylbenzene, 5-bromo-1,3-bis(α-hydroxyisopropyl)benzene, 2-methoxy-1,4-diisopropenylbenzene, 2-methoxy-1,4-bis(α-hydroxyisopropyl)benzene, 5-ethoxy-1,3-diisopropenylbenzene, 5-ethoxy-1,3-bis(α-hydroxyisopropyl)benzene, 2-phenoxy-1,4-diisopropenylbenzene, 2-phenoxy-1,4-bis(α-hydroxyisopropyl)benzene, 2,4-diisopropenylbenzenethiol, 2,4-biisopropenylbenzene, Bis(α-hydroxyisopropyl)benzenethiol, 2,5-diisopropenylbenzenethiol, 2,5-bis(α-hydroxyisopropyl)benzenethiol, 2-methylthio-1,4-diisopropenylbenzene, 2-methylthio-1,4-bis(α-hydroxyisopropyl)benzene, 2-phenylthio-1,3-diisopropenylbenzene, 2-phenylthio-1,3-bis(α-hydroxyisopropyl)benzene, 2-phenyl-1,4-diisopropenylbenzene, 2-phenyl-1,4-bis(α-hydroxyisopropyl)benzene Benzene, 2-cyclopentyl-1,4-diisopropenylbenzene, 2-cyclopentyl-1,4-bis(α-hydroxyisopropyl)benzene, 5-naphthyl-1,3-diisopropenylbenzene, 5-naphthyl-1,3-bis(α-hydroxyisopropyl)benzene, 2-methyl-1,4-diisopropenylbenzene, 2-methyl-1,4-bis(α-hydroxyisopropyl)benzene, 5-butyl-1,3-diisopropenylbenzene, 5-butyl-1,3-bis(α-hydroxyisopropyl)benzene, 5-cyclohexyl-1,Examples include 3-diisopropenylbenzene and 5-cyclohexyl-1,3-bis(α-hydroxyisopropyl)benzene.

[0036] In addition, the substituent contained in the compound (a) is not particularly limited, and the above-mentioned exemplary compounds can be used, but in the case of a substituent with a large steric hindrance, stacking of the obtained indane bisphenol compounds is less likely to occur and crystallization of the indane bisphenol compounds is less likely to occur compared to a substituent with a small steric hindrance, that is, the solvent solubility of the indane bisphenol compound is improved, which is a preferred embodiment. In addition, when the compound (a) is used as a raw material, as described in JP 2021-143333 A, the structural unit having the desired indane skeleton may also contain structural units (a) and (b) in formula (2) of the publication.

[0037] The compound represented by the general formula (6) (hereinafter referred to as "compound (b)") is a phenol or a derivative thereof, and is not particularly limited, but typically includes cresols such as o-cresol, m-cresol, and p-cresol; phenol; xylenols such as 2,3-xylenol, 2,4-xylenol, 2,5-xylenol, 2,6-xylenol, 3,4-xylenol, and 3,5-xylenol; ethylphenols such as o-ethylphenol, m-ethylphenol, and p-ethylphenol; butylphenols such as isopropylphenol, butylphenol, and pt-butylphenol; alkylphenols such as p-pentylphenol, p-octylphenol, p-nonylphenol, and p-cumylphenol; halogenated phenols such as fluorophenol, chlorophenol, bromophenol, and iodophenol; mono-substituted phenols such as p-phenylphenol, aminophenol, nitrophenol, dinitrophenol, and trinitrophenol; condensed polycyclic phenols such as 1-naphthol and 2-naphthol; resorcin, alkylresorcin, pyrogallol, and catechol. , polyhydric phenols such as alkylcatechol, hydroquinone, alkylhydroquinone, and phloroglucinone; various o-, m-, and p-isomers of alkylphenols such as pyrocatechol, isobutylphenol, sec-butylphenol, t-butylphenol, t-aminophenol, methyl-t-butylphenol, di-t-butylphenol, and di-t-amylphenol; various o-, m-, and p-isomers of alkenyl or alkynylphenols such as vinylphenol, allylphenol, propenylphenol, and ethynylphenol; various o-, m-, and p-isomers of alkoxy, alkenyloxy, or alkynyloxyphenols such as methoxyphenol, ethoxyphenol, allyloxyphenol, and propargyloxyphenol; cycloalkylphenols such as cyclopentylphenol, cyclohexylphenol, and cyclohexyl cresol; halogen-substituted phenols such as dichlorophenol and dibromophenol; other substituted phenols such as cyanophenol, arylphenol, and aralkylphenol;Examples of the phenols or derivatives thereof include alkylhydroquinone, alkenylresorcin, alkenylhydroquinone, alkyloxyresorcin, alkyloxyhydroquinone, haloresorcin, and halohydroquinone, and various substituted hydroquinones, 2-t-butyl-5-methylphenol, 2-t-butyl-4-methylphenol, 2,4-di(t-butyl)phenol, 2,4-di(t-amyl)phenol, 2-cyclohexyl-5-methylphenol, 2-t-butylphenol, 2-sec-butylphenol, 2-(t-amyl)phenol, and 2-cyclohexylphenol. These phenols or derivatives thereof may be used alone or in combination of two or more. Among them, it is more preferable to use a compound in which one or more of the ortho positions of the phenolic hydroxyl group, such as 2,6-xylenol or o-cresol, are substituted with alkyl. However, if the steric hindrance is too large, there is a concern that the reactivity during synthesis of the indane bisphenol compound may be inhibited, so it is preferable to use, for example, a compound (b) having an alkyl group having 1 to 4 carbon atoms.

[0038] In the method for producing an indane bisphenol compound represented by the general formula (7) used in the present invention, the compound (a) and the compound (b) are charged in a molar ratio of the compound (b) to the compound (a) (compound (b) / compound (a)) of preferably 0.1 to 10, more preferably 0.2 to 8.0, and reacted in the presence of an acid catalyst to obtain an indane bisphenol compound having an indane skeleton. Alternatively, the compound (a) may be used as a raw material to obtain an olefin resin as described in JP-A-2021-143333, and then reacted with the compound (b).

[0039] Examples of the acid catalyst used in the reaction include inorganic acids such as phosphoric acid, hydrochloric acid, and sulfuric acid; organic acids such as oxalic acid, benzenesulfonic acid, toluenesulfonic acid, methanesulfonic acid, and fluoromethanesulfonic acid; solid acids such as activated clay, acid clay, silica alumina, zeolite, and strongly acidic ion exchange resins; and heteropolyhydrochloric acids. However, it is preferable to use oxalic acid, benzenesulfonic acid, toluenesulfonic acid, methanesulfonic acid, and fluoromethanesulfonic acid (especially p-toluenesulfonic acid), which are homogeneous catalysts that can be easily removed by neutralization with a base and washing with water after the reaction.

[0040] The amount of the acid catalyst to be mixed is within a range of 0.001 to 40 parts by mass per 100 parts by mass of the total amount of the compound (a) and the compound (b) that are the raw materials initially charged, and from the viewpoint of economy, 0.001 to 5 parts by mass is preferable.

[0041] The reaction temperature is usually in the range of 50 to 300° C., but in order to suppress the formation of isomeric structures, avoid side reactions such as thermal decomposition, and obtain a high-purity indane bisphenol compound, a temperature of 80 to 200° C. is preferred.

[0042] The reaction time is usually in the range of 0.5 to 24 hours in total under the above reaction temperature conditions, and preferably in the range of 0.5 to 12 hours in total, since the reaction does not proceed completely in a short time and side reactions such as thermal decomposition of the product occur in a long time.

[0043] In the method for producing an indane bisphenol compound, since phenol or its derivative also serves as a solvent, other solvents are not necessarily used, but it is possible to use a solvent. For example, in the case of a reaction system also serving as a dehydration reaction, specifically, when a compound having an α-hydroxypropyl group is reacted as a raw material, a method may be adopted in which a solvent capable of azeotropic dehydration such as toluene, xylene, or chlorobenzene is used, the dehydration reaction is completed, the solvent is distilled off, and then the reaction is carried out within the above reaction temperature range.

[0044] Examples of organic solvents used for synthesizing the indane bisphenol compound include ketones such as acetone, methyl ethyl ketone (MEK), methyl isobutyl ketone, cyclohexanone, cyclopentanone, and acetophenone; aprotic solvents such as N,N-dimethylformamide, N,N-dimethylacetamide, dimethyl sulfoxide, N-methyl-2-pyrrolidone, acetonitrile, and sulfolane; cyclic ethers such as dioxane and tetrahydrofuran; esters such as ethyl acetate and butyl acetate; and aromatic solvents such as benzene, toluene, and xylene. These may be used alone or in combination.

[0045] From the viewpoint of heat resistance, the hydroxyl equivalent of the indane bisphenol compound is preferably 100 to 1000 g / eq, more preferably 150 to 800 g / eq. The hydroxyl equivalent of the indane bisphenol compound is calculated by a titration method, and refers to the neutralization titration method in accordance with JIS K 0070.

[0046] <Method of producing a vinylbenzyl compound having an indane bisphenol skeleton> Next, the introduction of a vinylbenzyl ether group into the indane bisphenol compound will be described below.

[0047] The vinylbenzyl compound having the indane bisphenol skeleton can be obtained by a known method such as reacting the polyindane bisphenol compound with chloromethylstyrene, bromomethylstyrene, or methylstyrene iodide in the presence of a basic compound. By reacting these, radical polymerization can be introduced into the polyindane bisphenol compound, and crosslinking with various crosslinking agents having low dielectric properties can be achieved. In addition, since it is a low polarity substituent, the cured product of the obtained resin exhibits low dielectric constant and low dielectric loss tangent.

[0048] The chloromethylstyrene may be, for example, p-chloromethylstyrene, m-chloromethylstyrene, or o-chloromethylstyrene. The bromomethylstyrene may be, for example, p-bromomethylstyrene, m-bromomethylstyrene, or o-bromomethylstyrene, and these may be used alone or in combination. Among them, it is preferable to use chloromethylstyrene, which is a cheaper raw material and can obtain a cured product with a low dielectric loss tangent.

[0049] Specific examples of the basic compound include nitrogen atom-containing compounds such as triethylamine, tributylamine, and dimethylaminopyridine, alkaline earth metal hydroxides, alkali metal carbonates, and alkali metal hydroxides, etc. In particular, alkali metal hydroxides are excellent in that they are highly active and inexpensive.

[0050] The reaction of the intermediate phenol compound with the chloromethylstyrene or chlorostyrene may be carried out by adding 1 to 10 moles of the chloromethylstyrene or chlorostyrene per mole of hydroxyl group contained in the intermediate phenol compound, and reacting for 1 to 40 hours at a temperature of 30 to 150° C. while adding 1 to 10 moles of a basic compound all at once or gradually. In this case, in order to improve the reaction rate, an interphase transfer catalyst such as an alkyl ammonium salt may be used in an amount of 0.1 to 20 parts by weight per 100 parts by weight of the resin produced.

[0051] In addition, by using an organic solvent in the reaction with chloromethylstyrene (introduction of a crosslinking group), the reaction rate in the synthesis of the vinylbenzyl compound having the polyindane bisphenol skeleton can be increased. Such organic solvents are not particularly limited, but examples thereof include ketones such as acetone and methyl ethyl ketone, alcohols such as methanol, ethanol, 1-propyl alcohol, isopropyl alcohol, 1-butanol, secondary butanol, and tertiary butanol, cellosolves such as methyl cellosolve and ethyl cellosolve, ethers such as tetrahydrofuran, 1,4-dioxane, 1,3-dioxane, and diethoxyethane, aprotic polar solvents such as acetonitrile, dimethyl sulfoxide, and dimethylformamide, toluene, and xylene. These organic solvents may be used alone, or two or more of them may be used in combination as appropriate to adjust the polarity.

[0052] After the above-mentioned reaction with chloromethylstyrene (introduction of a crosslinking group) is completed, water can be added to separate the mixture and remove the by-products as the aqueous layer in order to remove the alkali metal salts and catalyst residues produced by the reaction. These alkali metal salts and catalyst residues deteriorate the dielectric properties, so it is preferable to thoroughly wash them with water to remove them. Furthermore, after reprecipitating the reaction product in a poor solvent, the precipitate can be stirred in the poor solvent at a temperature of 20 to 100°C for 0.1 to 5 hours, filtered under reduced pressure, and then dried at a temperature of 40 to 80°C for 1 to 10 hours to further increase the purity. In this manner, the desired vinylbenzyl compound having an indane bisphenol skeleton (hereinafter, sometimes referred to as a curable resin) can be obtained. Examples of poor solvents include hexane.

[0053] <Polymerization inhibitor> It is essential that the curable resin composition of the present invention contains a specific amount of a polymerization inhibitor. In general, when a polymerization inhibitor is added to a curable resin having an indane bisphenol skeleton, the polymerization inhibitor has a highly polar substituent such as a phenolic hydroxyl group, and therefore the dielectric tangent and the like are thought to be significantly reduced. In addition, since it is a low molecular weight component and has a high effect of inhibiting polymerization, it also results in a loss of heat resistance. However, in the present invention, it has been found that excellent heat resistance and low dielectric properties can be achieved at the same time by introducing a vinylbenzyl group into the curable resin and using a specific amount of a polymerization inhibitor.

[0054] As the polymerization inhibitor, a known polymerization inhibitor can be used. Examples of the polymerization inhibitor include hindered phenol-based polymerization inhibitors (e.g., pyrogallol, benzoquinone, hydroquinone, methylene blue, tert-butylcatechol, monobenzyl ether, methylhydroquinone, amylquinone, amyloxyhydroquinone, n-butylphenol, phenol, hydroquinone monopropyl ether, 4,4'-(1-methylethylidene)bis(2-methylphenol), 4,4'-(1-methylethylidene)bis(2,6-dimethyl Phenol), 4,4'-[1-[4-(1-(4-hydroxyphenyl)-1-methylethyl)phenyl]ethylidene]bisphenol, 4,4',4"-ethylidene tris(2-methylphenol), 4,4',4"-ethylidene trisphenol, 1,1,3-tris(2,5-dimethyl-4-hydroxyphenyl)-3-phenylpropane, 2,6-di-tert-butyl-4-methylphenol, 2,2'-methylenebis(4-methyl-6-tert-butylphenol) ), 4,4'-butylidenebis(3-methyl-6-tert-butylphenol), 4,4'-thiobis(3-methyl-6-tert-butylphenol), 3,9-bis[2-(3-(3-tert-butyl-4-hydroxy-5-methylphenyl)-propionyloxy)-1,1-dimethylethyl]-2,4,8,10-tetraoxaspiro(5,5)undecane, triethylene glycol-bis-3-(3-tert-butyl-4-hydroxy-5-methylphenyl)propionyloxy dopionate, n-octyl-3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate, pentaerythryl tetrakis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate] (trade name IRGANOX1010, manufactured by BASF), tris(3,5-di-tert-butylhydroxybenzyl)isocyanurate, thiodiethylene bis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate], etc.);Phenol-based polymerization inhibitors other than hindered phenols (e.g., 4-methoxyphenol, 2,5-di-tert-butyl-4-methylphenol, 4,4'-thiobis(3-methyl-6-t-butylphenol), 2,2'-methylenebis(4-methyl-6-t-butylphenol), 4-methoxynaphthol, etc.) (collectively abbreviated as phenol-based polymerization inhibitors); hydroquinone-based polymerization inhibitors (e.g., hydroquinone, 2,6-di-tert-butylhydroquinone, etc.) can be used.

[0055] The polymerization inhibitor is preferably hydroquinone, trimethylhydroquinone, 4-tert-butylpyrocatechol, tert-butylhydroquinone, toluhydroquinone, parabenzoquinone, 4-methoxyphenol, or 2,6-di-tert-butyl-4-methylphenol, and more preferably 4-tert-butylpyrocatechol, parabenzoquinone, 4-methoxyphenol, or 2,6-di-tert-butyl-4-methylphenol, since the cured product described below has better heat resistance and dielectric properties.

[0056] The polymerization inhibitor may be used alone or in combination of two or more. However, it is preferable to contain two or more polymerization inhibitors (use two or more polymerization inhibitors in combination). When two or more polymerization inhibitors are used in combination, the combination of polymerization inhibitors is not particularly limited, but in terms of obtaining better effects of the present invention, a hindered phenol-based polymerization inhibitor and / or the other phenol-based polymerization inhibitors are preferable, and 4-methoxyphenol and / or 2,6-di-tert-butyl-4-methylphenol are more preferable.

[0057] When two types of polymerization inhibitors are contained, the mixing ratio is, for example, 5:95 to 95:5.

[0058] The content of the polymerization inhibitor is essential to be 50 to 5,000 ppm relative to the vinylbenzyl compound in order to obtain the effects of the present invention, and is preferably 100 to 5,000 ppm from the viewpoint of exhibiting the effects better and further improving the heat resistance and dielectric properties after curing. In other words, the content is 0.005 to 0.5 parts by mass, preferably 0.01 to 0.5 parts by mass, relative to 100 parts by mass of the vinylbenzyl compound.

[0059] <Curable resin composition> The curable resin composition of the present invention contains the vinylbenzyl compound and the polymerization inhibitor, and further contains a specific total chlorine content. The total chlorine content is 100 to 10,000 ppm, preferably 100 to 5,000 ppm, based on the total amount of the vinylbenzyl compound and the polymerization inhibitor. The total chlorine content indicates the total content of chlorine atoms and is derived from the raw material of the vinylbenzyl compound, and examples of sources include chloromethylstyrene, which is a raw material for vinylbenzylation, and impurities contained therein.

[0060] [Other resins, etc.] In addition to the above, other resins, curing agents, curing accelerators, etc. can be used in the curable resin composition of the present invention without any particular limitation, so long as the object of the present invention is not impaired. As described later, the curable resin can be cured by heating or the like without blending a curing agent, but when blending other resins, etc., for example, a curing agent, a curing accelerator, etc. can be blended and used.

[0061] [Other resins] Examples of the other resins that can be added include alkenyl group-containing compounds such as bismaleimides, allyl ether compounds, allyl amine compounds, triallyl isocyanurate, alkenyl phenol compounds, vinyl group-containing polyolefin compounds, etc. In addition, other thermosetting resins such as thermosetting polyimide resins, epoxy resins, phenolic resins, active ester resins, benzoxazine resins, cyanate ester resins, etc. can also be appropriately blended depending on the purpose.

[0062] [Hardening agent] Examples of the curing agent include amine compounds, amide compounds, acid anhydride compounds, phenol compounds, cyanate ester compounds, active ester resins, etc. These curing agents may be used alone or in combination of two or more kinds.

[0063] [Curing Accelerator] As the curing accelerator, various types can be used, including, for example, phosphorus compounds, tertiary amines, imidazoles, organic acid metal salts, Lewis acids, amine complex salts, etc. In particular, when used as a semiconductor encapsulation material, phosphorus compounds such as triphenylphosphine or imidazoles are preferred because of their excellent curability, heat resistance, electrical properties, and moisture resistance reliability. These curing accelerators can be used alone or in combination of two or more.

[0064] [Flame retardant] The curable resin composition of the present invention may contain a flame retardant to exhibit flame retardancy, if necessary, and preferably contains a non-halogen flame retardant that does not substantially contain halogen atoms. Examples of the non-halogen flame retardant include phosphorus-based flame retardants, nitrogen-based flame retardants, silicone-based flame retardants, inorganic flame retardants, and organic metal salt-based flame retardants, and these flame retardants may be used alone or in combination of two or more.

[0065] [Filler] The curable resin composition of the present invention may contain an inorganic filler as required. Examples of the inorganic filler include fused silica, crystalline silica, alumina, silicon nitride, and aluminum hydroxide. When the amount of the inorganic filler is particularly large, it is preferable to use fused silica. The fused silica may be either crushed or spherical, but in order to increase the amount of fused silica and suppress the increase in the melt viscosity of the molding material, it is preferable to mainly use spherical silica. In order to further increase the amount of spherical silica, it is preferable to appropriately adjust the particle size distribution of the spherical silica. In addition, when the curable resin composition is used for applications such as a conductive paste described in detail below, a conductive filler such as silver powder or copper powder can be used.

[0066] [Other compounding agents] To the curable resin composition of the present invention, various compounding agents such as a silane coupling agent, a release agent, a pigment, an emulsifier, etc. may be added, if necessary.

[0067] <Cured product> The present invention relates to a cured product obtained by subjecting the curable resin composition to a curing reaction. The curable resin composition can be obtained by uniformly mixing the curable resin alone or the curable resin and each component such as the curing agent described above, and can be easily cured by a method similar to a conventionally known method. Examples of the cured product include molded cured products such as laminates, cast products, adhesive layers, coatings, and films.

[0068] The curing reaction includes heat curing and ultraviolet curing reaction, among which heat curing reaction is easily carried out even without a catalyst, but when it is desired to react more quickly, it is effective to add a polymerization initiator such as an organic peroxide or an azo compound, or a basic catalyst such as a phosphine compound or a tertiary amine. For example, benzoyl peroxide, dicumyl peroxide, azobisisobutyronitrile, triphenylphosphine, triethylamine, imidazoles, etc.

[0069] <Application> The cured product obtained by the curable resin composition of the present invention has excellent heat resistance and dielectric properties, and therefore can be suitably used for heat-resistant members and electronic members. In particular, it can be suitably used for prepregs, circuit boards, semiconductor encapsulants, semiconductor devices, build-up films, build-up boards, adhesives, resist materials, etc. It can also be suitably used for matrix resins of fiber-reinforced resins, and is particularly suitable as highly heat-resistant prepregs. In addition, the curable resin contained in the curable resin composition exhibits excellent solubility in various solvents, and can be made into paint. The heat-resistant members and electronic members thus obtained can be suitably used for various applications, such as industrial machine parts, general machine parts, automobile, railway, vehicle parts, space and aviation related parts, electronic and electrical parts, building materials, containers and packaging materials, daily necessities, sports and leisure goods, and housing members for wind power generation, but are not limited thereto.

[0070] <Prepreg> The prepreg of the present invention preferably has a reinforcing substrate and a semi-cured product of the curable resin composition impregnated into the reinforcing substrate. The prepreg can be produced by a known method, but the curable resin composition can be dissolved (diluted) in an organic solvent, and the reinforcing substrate is impregnated with a resin varnish, and the reinforcing substrate impregnated with the resin varnish is heat-treated to semi-cure (or uncure) the curable resin composition, thereby producing a prepreg.

[0071] As the organic solvent, for example, toluene, xylene, N,N-dimethylformamide, N,N-dimethylacetamide, N-methyl-2-pyrrolidone, methyl ethyl ketone (MEK), methyl isobutyl ketone, dioxane, tetrahydrofuran, etc. can be used alone or as a mixed solvent of two or more kinds.

[0072] The reinforcing substrate to be impregnated with the resin varnish may be a woven or nonwoven fabric made of inorganic fibers such as glass fibers, polyester fibers, or polyamide fibers, or an organic fiber, or a mat, paper, or the like, and these may be used alone or in combination.

[0073] The mass ratio of the curable resin composition to the reinforcing base material in the prepreg is not particularly limited, but it is usually preferable to prepare the prepreg so that the curable resin composition (resin content therein) is 20 to 80 mass %.

[0074] The conditions for the heat treatment of the prepreg are appropriately selected depending on the types and amounts of the organic solvent, catalyst, and various additives used, but the heat treatment is usually performed at a temperature of 80 to 220° C. for 3 to 30 minutes.

[0075] <Heat-resistant materials and electronic materials> The cured product obtained by the curable resin composition of the present invention has excellent heat resistance and dielectric properties, and therefore can be suitably used for heat-resistant members and electronic members. In particular, it can be suitably used for circuit boards, semiconductor encapsulants, semiconductor devices, build-up films, build-up substrates, adhesives, resist materials, etc. It can also be suitably used for matrix resins of fiber-reinforced resins, and is particularly suitable as highly heat-resistant prepregs. In addition, the vinyl benzyl compound contained in the curable resin composition exhibits excellent solubility in various solvents, and can be made into paint. The heat-resistant members and electronic members thus obtained can be suitably used for various applications, such as industrial machine parts, general machine parts, automobile, railway, vehicle parts, space and aviation related parts, electronic and electrical parts, building materials, containers and packaging materials, daily necessities, sports and leisure goods, and housing members for wind power generation, but are not limited thereto.

[0076] Representative products produced using the curable resin composition of the present invention will be described below with reference to examples.

[0077] <Circuit board> In the present invention, the circuit board is preferably obtained by laminating the prepreg and copper foil, and subjecting them to thermocompression molding. Specifically, a method for obtaining a circuit board from the curable resin composition of the present invention includes a method in which the prepreg is laminated by a conventional method, copper foil is appropriately layered, and the resultant is subjected to thermocompression molding at 170 to 300° C. under a pressure of 1 to 10 MPa for 10 minutes to 3 hours.

[0078] <Semiconductor encapsulation material> In the present invention, the semiconductor encapsulant preferably contains the curable resin composition. Specifically, as a method for obtaining a semiconductor encapsulant from the curable resin composition of the present invention, the curable resin composition is further mixed with optional components such as a curing accelerator and an inorganic filler by using an extruder, kneader, roll, or the like until the mixture is homogeneous. In this case, fused silica is usually used as the inorganic filler, but when used as a high thermal conductivity semiconductor encapsulant for power transistors and power ICs, it is preferable to use highly filled crystalline silica, alumina, silicon nitride, etc., which have a higher thermal conductivity than fused silica, or fused silica, crystalline silica, alumina, silicon nitride, etc. The filling rate is preferably in the range of 30 to 95 parts by mass per 100 parts by mass of the curable resin composition, and in particular, in order to improve flame retardancy, moisture resistance, and solder crack resistance and to reduce the linear expansion coefficient, it is more preferable to use 70 parts by mass or more, and even more preferable to use 80 parts by mass or more.

[0079] <Semiconductor device> In the present invention, the semiconductor device preferably includes a cured product obtained by heat-curing the semiconductor encapsulant. Specifically, the semiconductor package molding for obtaining a semiconductor device from the curable resin composition of the present invention includes a method in which the semiconductor encapsulant is molded by casting or using a transfer molding machine, an injection molding machine, or the like, and then heat-cured at 50 to 250° C. for 2 to 10 hours.

[0080] <Build-up board> The method for obtaining a build-up board from the curable resin composition of the present invention includes a method via steps 1 to 3. In step 1, the curable resin composition containing rubber, filler, etc. is first applied to a circuit board on which a circuit is formed by using a spray coating method, a curtain coating method, etc., and then cured. In step 2, if necessary, the circuit board on which the curable resin composition is applied is drilled for a predetermined through-hole portion, etc., and then treated with a roughening agent, and the surface is washed with hot water to form unevenness on the board, and a metal such as copper is plated. In step 3, the operations of steps 1 and 2 are repeated in sequence as desired, and a resin insulating layer and a conductor layer of a predetermined circuit pattern are alternately built up to form a build-up board. In the above steps, the through-hole portion is preferably drilled after the formation of the outermost resin insulating layer. In addition, the build-up board of the present invention can be produced by forming a roughened surface and omitting the plating process by heating and pressing the resin-coated copper foil, which is prepared by semi-curing the resin composition on the copper foil, onto a wiring board on which a circuit has been formed, at 170 to 300°C.

[0081] <Build-up film> The build-up film of the present invention preferably contains the curable resin composition. As a method for obtaining a build-up film from the curable resin composition of the present invention, for example, a method of applying the curable resin composition on a support film, drying the composition, and forming a resin composition layer on the support film can be mentioned. When the curable resin composition of the present invention is used for a build-up film, it is essential that the film softens under the temperature conditions for lamination in the vacuum lamination method (usually 70 to 140°C), and exhibits a fluidity (resin flow) that allows resin filling in via holes or through holes present in the circuit board at the same time as lamination of the circuit board, and it is preferable to mix the above-mentioned components so as to express such characteristics.

[0082] Here, the diameter of the through-hole in the circuit board is usually 0.1 to 0.5 mm, and the depth is usually 0.1 to 1.2 mm, and it is usually preferable to enable resin filling within this range.

[0083] A specific method for producing the build-up film described above includes preparing a resin composition varnished by blending an organic solvent, applying the varnished resin composition to the surface of a support film (Y), and then drying the organic solvent by heating or blowing hot air or the like to form a resin composition layer (X).

[0084] The organic solvent used here preferably includes, for example, ketones such as acetone, methyl ethyl ketone, cyclohexanone, etc., acetate esters such as ethyl acetate, butyl acetate, cellosolve acetate, propylene glycol monomethyl ether acetate, carbitol acetate, etc., carbitols such as cellosolve, butyl carbitol, etc., aromatic hydrocarbons such as toluene, xylene, etc., dimethylformamide, dimethylacetamide, N-methylpyrrolidone, etc., and it is preferable to use the organic solvent in a proportion such that the nonvolatile content is 30 to 60 mass%.

[0085] The thickness of the resin composition layer (X) formed is usually required to be equal to or greater than the thickness of the conductor layer. Since the thickness of the conductor layer of the circuit board is usually in the range of 5 to 70 μm, the thickness of the resin composition layer (X) is preferably 10 to 100 μm. The resin composition layer (X) in the present invention may be protected with a protective film described below. By protecting the resin composition layer with a protective film, adhesion of dirt and the like to the surface of the resin composition layer and scratches can be prevented.

[0086] The above-mentioned support film and protective film may be made of polyolefins such as polyethylene, polypropylene, and polyvinyl chloride, polyesters such as polyethylene terephthalate (PET) and polyethylene naphthalate, polycarbonate, polyimide, and even release paper and metal foils such as copper foil and aluminum foil. The support film and protective film may be subjected to a release treatment in addition to a mud treatment and a corona treatment. The thickness of the support film is not particularly limited, but is usually 10 to 150 μm, and is preferably used in the range of 25 to 50 μm. The thickness of the protective film is preferably 1 to 40 μm.

[0087] The support film (Y) is peeled off after laminating it onto a circuit board or after forming an insulating layer by heat curing. If the support film (Y) is peeled off after the resin composition layer constituting the build-up film is heat cured, adhesion of dust and the like during the curing process can be prevented. When peeling off after curing, the support film is usually subjected to a release treatment in advance.

[0088] A multilayer printed circuit board can be manufactured from the build-up film obtained as described above. For example, when the resin composition layer (X) is protected by a protective film, the protective film is peeled off, and then the resin composition layer (X) is laminated on one or both sides of the circuit board so as to be in direct contact with the circuit board, for example, by a vacuum lamination method. The lamination method may be a batch method or a continuous method using a roll. If necessary, the build-up film and the circuit board may be heated (preheated) before lamination. The lamination conditions are preferably a pressure bonding temperature (lamination temperature) of 70 to 140°C and a pressure bonding pressure of 1 to 11 kgf / cm. 2 (9.8×10 4 ~107.9×10 4 N / m 2 ), and lamination is preferably performed under reduced air pressure of 20 mmHg (26.7 hPa) or less.

[0089] <Conductive paste> A method for obtaining a conductive paste from the curable resin composition of the present invention includes, for example, dispersing conductive particles in the composition. The conductive paste can be a paste resin composition for circuit connection or an anisotropic conductive adhesive depending on the type of conductive particles used.

[0090] Examples of the present invention are shown below, but the present invention is not limited thereto. The present invention will be specifically described with reference to Examples and Comparative Examples, in which "parts" and "%" are by mass unless otherwise specified. A curable resin and a curable resin composition containing the curable resin were used to synthesize a cured product under the conditions shown below, and the obtained cured product was measured and evaluated under the conditions shown below.

[0091] <Measuring method for the number of repeating units n> The following measuring apparatus and measuring conditions were used to measure, and GPC charts of vinylbenzyl compounds (B-1) to (B-3) having an indane bisphenol skeleton obtained in the following synthesis examples were obtained. From the results of the GPC charts, the average number of repeating units n contributing to the indane skeleton in the indane bisphenol compound was calculated based on the number average molecular weight (Mn) of the indane bisphenol compound. Specifically, for compounds with n of 0 to 4, the theoretical molecular weight and each measured molecular weight in GPC were plotted on a scatter diagram, an approximation line was drawn, and the number average molecular weight (Mn) was calculated from the point indicated by the measured value Mn (1) on the line.

[0092] Measurement equipment: Tosoh Corporation "HLC-8320 GPC" Column: Tosoh Corporation guard column "HXL-L" + Tosoh Corporation "TSK-GEL G2000HXL" + Tosoh Corporation "TSK-GEL G2000HXL" + Tosoh Corporation "TSK-GEL G3000HXL" + Tosoh Corporation "TSK-GEL G4000HXL" Detector: RI (differential refractometer) Data processing: Tosoh Corporation's "GPC Workstation EcoSEC-WorkStation" Measurement conditions: Column temperature 40℃ Developing solvent: Tetrahydrofuran Flow rate 1.0ml / min Standard: In accordance with the measurement manual for the "GPC Workstation EcoSEC-WorkStation," the following monodisperse polystyrene with known molecular weight was used.

[0093] (Polystyrene used) "A-500" manufactured by Tosoh Corporation "A-1000" manufactured by Tosoh Corporation "A-2500" manufactured by Tosoh Corporation "A-5000" manufactured by Tosoh Corporation "F-1" manufactured by Tosoh Corporation "F-2" manufactured by Tosoh Corporation "F-4" manufactured by Tosoh Corporation "F-10" manufactured by Tosoh Corporation "F-20" manufactured by Tosoh Corporation "F-40" manufactured by Tosoh Corporation "F-80" manufactured by Tosoh Corporation "F-128" manufactured by Tosoh Corporation Sample: A tetrahydrofuran solution (1.0 mass % in terms of solid content) of the vinylbenzyl compounds (B-1) to (B-3) having an indane bisphenol skeleton obtained in the synthesis examples shown below was filtered through a microfilter (50 μl).

[0094] <Measurement of hydroxyl group concentration> The hydroxyl value was measured according to a method in accordance with JIS K 0070:1992, and the hydroxyl equivalent (g / eq) was calculated based on the formula 1000×56.11 / hydroxyl value.

[0095] Synthesis Example 1 (Synthesis of indane bisphenol compound (A-1)) In a flask equipped with a stirrer, a Dean-Stark apparatus, a cooling tube, and a nitrogen inlet, 244 parts of 2,6-xylenol, 388 parts of m-bis(α-hydroxyisopropyl)benzene, 633 parts of toluene, and 19 parts of paratoluenesulfonic acid monohydrate were charged and heated while blowing in nitrogen gas. During the reaction, the temperature was raised to 120°C while removing water generated by the reaction using a Dean-Stark apparatus, and the temperature was held for 10 hours. After cooling the reaction liquid, it was neutralized using a 49% aqueous sodium hydroxide solution until the pH was neutral. After removing the catalyst residue by washing with water, the volatile matter was distilled off by heating and reducing the pressure, and indane bisphenol (A-1) was obtained. The hydroxyl group equivalent of the obtained indane bisphenol (A-1) was 342 g / eq.

[0096] Synthesis Example 2 (Synthesis of polyindane bisphenol (A-2)) In a flask equipped with a stirrer, a Dean-Stark apparatus, a cooling tube, and a nitrogen inlet, 244 parts of 2,6-xylenol, 777 parts of m-bis(α-hydroxyisopropyl)benzene, 1022 parts of toluene, and 31 parts of paratoluenesulfonic acid monohydrate were used to carry out the same operation as in Synthesis Example 1 while blowing in nitrogen gas into the flask, to obtain indane bisphenol (A-2). The hydroxyl equivalent of the obtained indane bisphenol (A-2) was 580 g / eq.

[0097] Synthesis Example 3 (Synthesis of indane bisphenol (A-3)) In a flask equipped with a stirrer, a Dean-Stark apparatus, a cooling tube, and a nitrogen inlet, 244 parts of 2,6-xylenol, 194 parts of m-bis(α-hydroxyisopropyl)benzene, 439 parts of toluene, and 13 parts of paratoluenesulfonic acid monohydrate were used to carry out the same operation as in Synthesis Example 1 while blowing in nitrogen gas into the flask, to obtain an indane bisphenol compound (A-3). The hydroxyl equivalent of the obtained indane bisphenol (A-3) was 299 g / eq.

[0098] [ka] (A)

[0099] Synthesis Example 4 (Vinylbenzyl modification of indane bisphenol (A-1)) In a flask equipped with a stirrer, a Dean-Stark apparatus and a cooling tube, 100 parts of indane bisphenol (A-1), 74 parts of isopropanol, 172 parts of toluene, 49 parts of chloromethylstyrene (product name CMS-P, manufactured by AGC Seimi Chemical Co., Ltd.), and 0.8 parts of tetrabutylammonium bromide were charged and heated to 75°C while stirring to dissolve. 79 parts of 49% aqueous sodium hydroxide solution were added dropwise over 30 minutes, and the reaction was continued for 5 hours. After removing salts and catalyst residues from the reaction solution by washing with water, the volatile content was adjusted by heating and reducing the pressure, and a toluene solution of a vinylbenzyl compound (B-1) having an indane bisphenol skeleton was obtained. The number of repeating units n was 0.4.

[0100] Synthesis Example 5 (Vinylbenzyl modification of indanbisphenol (A-2)) In a flask equipped with a stirrer, a Dean-Stark apparatus and a cooling tube, 100 parts of indane bisphenol (A-2), 64 parts of isopropanol, 149 parts of toluene, 29 parts of chloromethylstyrene (product name CMS-P, manufactured by AGC Seimi Chemical Co., Ltd.), and 0.6 parts of tetrabutylammonium bromide were charged and heated to 75°C while stirring to dissolve. 46 parts of 49% aqueous sodium hydroxide solution were added dropwise over 30 minutes, and the reaction was continued for 5 hours. After removing salts and catalyst residues from the reaction solution by washing with water, the volatile content was adjusted by heating and reducing the pressure, and a toluene solution of vinylbenzyl compound (B-2) having an indane bisphenol skeleton was obtained. The number of repeating units n was 2.0.

[0101] Synthesis Example 6 (Vinylbenzyl modification of indane bisphenol (A-3)) In a flask equipped with a stirrer, a Dean-Stark apparatus and a cooling tube, 100 parts of indane bisphenol (A-3), 77 parts of isopropanol, 180 parts of toluene, 56 parts of chloromethylstyrene (product name CMS-P, manufactured by AGC Seimi Chemical Co., Ltd.), and 0.8 parts of tetrabutylammonium bromide were charged and heated to 75°C while stirring to dissolve. 90 parts of 49% aqueous sodium hydroxide solution were added dropwise over 30 minutes, and the reaction was continued for 5 hours. After removing salts and catalyst residues from the reaction solution by washing with water, the volatile content was adjusted by heating and reducing the pressure, and a toluene solution of a vinylbenzyl compound (B-3) having an indane bisphenol skeleton was obtained. The number of repeating units n was 0.2.

[0102] [ka] (B)

[0103] Synthesis Example 7 (Vinylbenzyl modification of indanbisphenol (A-2)) In a flask equipped with a stirrer and a cooling tube, 100 parts (0.172 equivalents) of polyindanbisphenol (A-2), 165 parts of dimethyl sulfoxide, 135 parts of tetrahydrofuran, 7.2 parts of powdered sodium hydroxide, and 0.17 g of methylhydroquinone were added and stirred at 40°C for 1 hour. 27.3 parts of chloromethylstyrene (product name CMS-P, manufactured by AGC Seimi Chemical Co., Ltd.) were added dropwise over 1 hour, and the temperature was raised to 80°C and the reaction was continued for 14 hours. The reaction solution was diluted with 300 g of toluene, and the salt, catalyst residue, dimethyl sulfoxide, and tetrahydrofuran were removed from the reaction solution by washing with water, and the volatile content was adjusted by heating and reducing the pressure, and a toluene solution of a vinylbenzyl compound (B-4) having an indanbisphenol skeleton was obtained. The number of repeating units n was 2.0.

[0104] Synthesis Example 8 (Purification of vinylbenzyl compound (B-2)) 1000 parts of methanol was added at room temperature to 200 parts of a toluene solution (non-volatile content 50%) of a vinylbenzyl compound having an indane bisphenol skeleton obtained in the same manner as in Synthesis Example 5 to precipitate a resin. The supernatant was removed by decantation to obtain a precipitate. This precipitate was dissolved again in 100 parts of toluene, and then 1000 parts of methanol was added to precipitate a resin. The supernatant was removed by decantation to obtain a purified resin as a precipitate. After dissolving again in toluene, the volatile content was adjusted by heating and reducing pressure to obtain a toluene solution of a vinylbenzyl compound (B-5) having an indane bisphenol skeleton. The number of repeating units n was 3.0.

[0105] Synthesis Example 9 (Synthesis of vinylbenzyl compound (B-6)) In a 2L flask equipped with a thermometer, a cooling tube, and a stirrer, 365.3 g of the intermediate phenol compound obtained, 0.184 g (0.001 mol) of 2,4-dinitrophenol (2,4-DNP), 23.5 g (0.073 mol) of tetrabutylammonium bromide (TBAB), 209 g (1.37 mol) of chloromethylstyrene, and 400 g of methyl ethyl ketone were added and heated to 75 ° C. while stirring. Next, 48%-NaOHaq was added dropwise to the reaction vessel kept at 75 ° C. over 20 minutes. After the dropwise addition, stirring was continued for another 4 hours at 75 ° C. After 4 hours, it was cooled to room temperature, 100 g of toluene was added, and 10% HCl was added for neutralization. Then, the aqueous phase was separated by liquid separation, and further washed with 300 m of water three times. The obtained organic phase was concentrated by distillation, and the product was reprecipitated by adding methanol. The precipitate was filtered and dried to obtain a vinylbenzyl compound (B-6) having an indane bisphenol skeleton (average number of repeating units n = 1.6).

[0106] <Measurement of total chlorine content> 0.3 g of the vinylbenzyl compound having an indane bisphenol skeleton obtained in the synthesis example was precisely weighed into a 200 ml Erlenmeyer flask with a stopper, 20 ml of 1-butanol was added, and the solution was refluxed and dissolved in an oil bath at 120°C. 1 g of metallic sodium was then added and refluxed in an oil bath for 1 hour. After cooling, 5 ml of pure water and 5 ml of nitric acid were added, and the NaCl generated in this solution was titrated with a 0.01 mol / L silver nitrate aqueous solution using a potentiometric titrator (Kyoto Electronics Manufacturing Co., Ltd., "AT-310J") to determine the NaCl content.

[0107] <Preparation of cured product> A curable resin composition containing a toluene solution of the vinylbenzyl compound having an indane bisphenol skeleton obtained in the synthesis example and 4-methoxyphenol (MQ) and 2,6-di-tert-butyl-4-methylphenol (BHT) as polymerization inhibitors in the amounts shown in Tables 1 and 2 was applied to a PET film using a 10-mil applicator and dried at 120°C for 10 minutes. The resulting thin film was collected, packed into a mold, and then heated at 200°C for 2 hours while applying a pressure of 4.9 MPa in a vacuum heat press to obtain a cured product. This was then cut out to prepare a test piece.

[0108] <Evaluation of heat resistance (glass transition temperature Tg)> The obtained cured product was cut into a size of 55 mm long x 5 mm wide x 1.6 mm thick to prepare a test piece. The test piece was evaluated using a viscoelasticity measuring device (DMA: Hitachi High-Tech Science Corporation solid viscoelasticity measuring device "DMS6100", deformation mode: double-support bending, measurement mode: sine wave vibration, frequency 1 Hz, heating rate 3°C / min), and the temperature at which the change in elastic modulus was maximum was determined as the glass transition temperature Tg. Note that as for the glass transition temperature (Tg), if it is 100°C or higher, there is no practical problem, and it is preferably 150°C or higher.

[0109] <Evaluation of dielectric properties> In accordance with JIS-C-6481, the dielectric constant and dielectric loss tangent of the test pieces at 10 GHz were measured using the cavity resonance method with an Agilent Technologies network analyzer "E8362C" after drying and storing them indoors at 23°C and 50% humidity for 24 hours.

[0110] [Table 1]

[0111] [Table 2]

[0112] [Table 3]

[0113] From the evaluation results in Tables 1 to 3, it was confirmed that in the examples, the cured products exhibited high heat resistance and low dielectric properties.

[0114] On the other hand, from the evaluation results of Tables 1 to 3, it was confirmed that in Comparative Examples 1 to 3, since no polymerization inhibitor was used, oxidation of the cured product could not be suppressed, and therefore the dielectric properties were higher than those of the Examples. Furthermore, even though a polymerization inhibitor was used, the total chlorine content in Comparative Example 4 was 50 ppm or less, and the total chlorine content in Comparative Example 5 was 5300 ppm, so both the heat resistance and the dielectric properties were inferior to those of the Examples. Comparative Example 6, which did not use a polymerization inhibitor and further had a total chlorine content of 50 ppm or less, also had a result of being inferior to those of the Examples in both heat resistance and dielectric properties.

[0115] From the evaluation results in Table 3, it was confirmed that the dielectric properties were higher than those of the examples in Comparative Example 7 because MQ and BHT were blended in excess. Therefore, it was confirmed that it is important to blend an appropriate amount of polymerization inhibitor. [Industrial Applicability]

[0116] The cured product obtained by blending a polymerization inhibitor with the vinylbenzyl compound having a polyindane bisphenol skeleton of the present invention has excellent heat resistance and dielectric properties, and therefore can be suitably used for heat-resistant parts and electronic parts, particularly for prepregs, semiconductor encapsulants, circuit boards, build-up films, build-up boards, adhesives, resist materials, etc. It can also be suitably used as a matrix resin for fiber-reinforced resins, and is suitable as a highly heat-resistant prepreg.

Claims

1. A curable resin composition containing a vinylbenzyl compound having an indane bisphenol skeleton represented by the following general formula (1): the curable resin composition further contains a polymerization inhibitor, and the content of the polymerization inhibitor is 50 to 5,000 ppm relative to the vinylbenzyl compound; A curable resin composition having a total chlorine content of 100 to 5000 ppm based on the total amount of the vinylbenzyl compound and the polymerization inhibitor. 【Chemistry 1】 ・・・・（１） [In formula (1), X represents a vinylbenzyloxy group. Each Ra independently represents an alkyl group having 1 to 15 carbon atoms, an alkyloxy group, an alkylthio group, an aralkyl group, an aryl group, an aryloxy group, an arylthio group, a cycloalkyl group, a hydrogen atom, a halogen atom, a nitro group, a hydroxyl group, or a mercapto group, and q represents an integer value of 0 to 4. When q is 2 to 4, Ra may be the same or different within the same ring. Each Rb independently represents an alkyl group having 1 to 15 carbon atoms, an alkyloxy group, an alkylthio group, an aryl group, an aryloxy group, an arylthio group, a cycloalkyl group, a hydrogen atom, a halogen atom, a hydroxyl group, or a mercapto group, and r represents an integer value of 0 to 3. When r is 2 to 3, Rb may be the same or different within the same ring. n is the average number of repeating units, and represents a numerical value of 0.2 to 20.]

2. The curable resin composition according to claim 1, wherein the vinylbenzyl compound is represented by the following general formula (2): 【Chemistry 2】 ・・・・（２） In the formula (2), X represents a vinylbenzyloxy group. １ and R ２ are each independently a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, an aryl group, an aralkyl group, or a cycloalkyl group, and R １ and R ２ are not both hydrogen atoms at the same time, and n is the average number of repeating units and is a value from 0.2 to 20.

3. 2. The curable resin composition according to claim 1, wherein the polymerization inhibitor is a phenol-based polymerization inhibitor.

4. A cured product obtained by subjecting the curable resin composition according to claim 1 to a curing reaction.

5. A prepreg comprising a reinforcing substrate and the curable resin composition according to claim 1 impregnated into the reinforcing substrate.

6. A circuit board obtained by laminating the prepreg according to claim 5 and copper foil, and subjecting the laminate to thermocompression molding.

7. A build-up film comprising the curable resin composition according to claim 1.

8. A semiconductor encapsulant comprising the curable resin composition according to claim 1.

9. A semiconductor device comprising a cured product obtained by heat-curing the semiconductor encapsulation material according to claim 8.

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